二维自组装聚合制备寡层有机-氧化硅纳米杂化材料
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摘要
设计、合成了一种两亲性硅氧烷前驱体(PABI),一端为羧基,另一端为具有反应性的硅氧烷基团.利用两亲性分子在水溶液中的自组装特性,研究了它的"二维自组装聚合".实验结果表明,PABI的二维自组装聚合行为与介质、碱的种类和碱的用量等因素有关.我们发现用四甲基胍(TMG)为碱时,PABI在水中通过自组装聚合可以形成寡层二维有机-氧化硅纳米杂化材料.透射电子显微镜(TEM)和原子力显微镜(AFM)的测试结果显示,片层的尺寸为几百纳米到几微米,片层的厚度为6～9 nm.当在水/有机溶剂(如DMSO、DMF、THF或MeOH)的混合溶液中进行自组装聚合时,均未得到层状结构的杂化材料.当用三乙胺和氢氧化钠为碱时,在水中只能得到多层堆积的杂化材料.本研究结果表明,通过二维自组装聚合,可以获得寡层甚至单层二维有机-氧化硅杂化材料.
It is still a challenge to prepare single-layered or few-layered organic-silica hybrid nanomaterials now.In this study, we designed and synthesized an amphiphilic organosilane(PABI) with phenyl urea and carboxyl groups, and investigated its two-dimensional self-assembly and polymerization. The spontaneous formation of few-layered organic-silica hybrid nanomaterials was driven by synergetic association of the hydrophobic interactions, π-π stacking interactions, hydrogen-bond interactions, electrostatic repulsion and hydrolytic condensation of the precursor under the appropriate conditions. The results indicated that the two-dimensional self-assembly and the polymerization were related to the experimental conditions, such as the medium, the type and the content of the base. The structure of the hybrid nanomaterials was demonstrated by nuclear magnetic resonance(1 H-NMR), Fourier transform infrared spectroscopy(FTIR) and 29 Si cross-polarization magic-angle spinning nuclear magnetic resonance(CP-MAS 29 Si-NMR). The morphology of the hybrid nanomaterials was confirmed by electron microscopy. Two or three layered organic-silica hybrid nanomaterials were obtained by two-dimensional self-assembly and polymerization of PABI in water when using 1,1,3,3-tetramethylguanidine(TMG) as a base under suitable condition(mole ratio of TMG to PABI was 1.1:1 or 1.5:1). The laminated sheet of the materials, with lateral size ranging from several hundred nanometers to several micrometers and thickness of 6 –9 nm, was demonstrated by transmission electron microscopy(TEM) and atomic force microscopy(AFM).However, when the content of TMG(mole ratio of TMG to PABI was 2:1) was too high, irregular aggregates were formed. In addition, irregular hybrid materials were obtained when organic solvents, such as DMF, DMSO, THF and MeOH, were respectively added to water. Moreover, when trimethylamine(TEA) and sodium hydroxide(NaOH) were used as bases, thick laminated sheets were obtained, and the result was consistent with X-ray diffraction spectrogram(XRD). These results are of great significance for preparation of few-layered or singlelayered organic-silica hybrid nanomaterials.
It is still a challenge to prepare single-layered or few-layered organic-silica hybrid nanomaterials now.In this study, we designed and synthesized an amphiphilic organosilane(PABI) with phenyl urea and carboxyl groups, and investigated its two-dimensional self-assembly and polymerization. The spontaneous formation of few-layered organic-silica hybrid nanomaterials was driven by synergetic association of the hydrophobic interactions, π-π stacking interactions, hydrogen-bond interactions, electrostatic repulsion and hydrolytic condensation of the precursor under the appropriate conditions. The results indicated that the two-dimensional self-assembly and the polymerization were related to the experimental conditions, such as the medium, the type and the content of the base. The structure of the hybrid nanomaterials was demonstrated by nuclear magnetic resonance(1 H-NMR), Fourier transform infrared spectroscopy(FTIR) and 29 Si cross-polarization magic-angle spinning nuclear magnetic resonance(CP-MAS 29 Si-NMR). The morphology of the hybrid nanomaterials was confirmed by electron microscopy. Two or three layered organic-silica hybrid nanomaterials were obtained by two-dimensional self-assembly and polymerization of PABI in water when using 1,1,3,3-tetramethylguanidine(TMG) as a base under suitable condition(mole ratio of TMG to PABI was 1.1:1 or 1.5:1). The laminated sheet of the materials, with lateral size ranging from several hundred nanometers to several micrometers and thickness of 6 –9 nm, was demonstrated by transmission electron microscopy(TEM) and atomic force microscopy(AFM).However, when the content of TMG(mole ratio of TMG to PABI was 2:1) was too high, irregular aggregates were formed. In addition, irregular hybrid materials were obtained when organic solvents, such as DMF, DMSO, THF and MeOH, were respectively added to water. Moreover, when trimethylamine(TEA) and sodium hydroxide(NaOH) were used as bases, thick laminated sheets were obtained, and the result was consistent with X-ray diffraction spectrogram(XRD). These results are of great significance for preparation of few-layered or singlelayered organic-silica hybrid nanomaterials.
引文
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2Lambert S,Tran K Y,Arrachart G,Noville F,Henrist C,Bied C,Moreau J J E,Man M W C,Heinrichs B.Micropor Mesopor Mat,2008,115(3):609-617
3Sanchez C,Belleville P,Popall M,Nicole L.Chem Soc Rev,2011,40(2):696-753
4Wang F K,Lu X,He C.J Mater Chem,2011,21(9):2775-2782
5Yu X,Zhong S,Li X,Tu Y,Wang S,Horn R M V,Ni C,Pochan D J,Quirk R P,Wesdemiotis C,Zhang W B,Cheng S Z D.J Am Chem Soc,2010,132(47):16741-16744
6Toyodome H,Kaneko Y,Shikinaka K,Iyi L.Polymer,2012,53(26):6021-6026
7Chemtob A,Ni L,Croutxé-Barghorn C,Boury B.Chem Eur J,2014,20(7):1790-1806
8Mehdi A,Reye C,Corriu R.Chem Soc Rev,2011,40(2):563-574
9Shimojima A,Kuroda K.Chem Rec,2006,6(2):53-63
10Kuroda K,Shimojima A,Kawahara K,Wakabayashi R,Tamura Y,Asakura Y,Kitahara M.Chem Mater,2013,26(1):211-220
11Croutxé-Barghorn C,Chemtob A,Ni L,Deroche I.Polym Int,2017,66(5):640-646
12Besson E,Mehdi A,ReyéC,Gaveaub P,Corriua R J P.Dalton Trans,2010,39(32):7534-7539
13Jiang J,Lima O V,Pei Y,Zeng X C,Tan L,Forsythe E.J Am Chem Soc,2009,131(3):900-901
14Besnard R,Arrachart G,Cambedouzou J,Pellet-Rostaing S.RSC Adv,2015,5(71):57521-57531
15Besnard R,Arrachart G,Cambedouzou J,Pellet-Rostaing S.Langmuir,2016,32(18):4624-4634
16Mouawia R,Mehdi A,ReyéC,Corriu R.J Mater Chem,2007,17(7):616-618
17Mouawia R,Mehdi A,ReyéC,Corriu R J P.J Mater Chem,2008,18(17):2028-2035
18Besson E,Mehdi A,Chollet H,RéyéC,Guilard R,Corriu R J P.J Mater Chem,2008,18(11):1193-1195
19Jiang J,Lima O V,Pei Y,Jiang Z,Chen Z,Yu C,Wang J,Zeng X C,Forsythe E,Tan L.ACS Nano,2010,4(7):3773-3780
20Li H,Kang J,Yang J,Wu B.J Phys Chem C,2016,120(30):16907-16912
21Alauzun J,Mehdi A,ReyéC,Corriu R.J Mater Chem,2005,15(8):841-843
22Ni B,Huang M,Chen Z,Chen Y,Hsu C,Li Y,Pochan D,Zhang W,Cheng S Z D,Dong X.J Am Chem Soc,2015,137(4):1392-1395
23Barboiu M,Cerneaux S,van der Lee A,Vaughan G.J Am Chem Soc,2004,126(11):3545-3550
24Zhang N,Wang T,Wu X,Jiang C,Zhang T,Jin B,Ji H,Bai W,Bai R.ACS Nano,2017,11(7):7223-7229
25Li Z,Tang M,Dai J,Wang T,Wang Z,Bai W,Bai R.Macromolecules,2017,50(11):4292-4299